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Published byLillian Hardy Modified over 8 years ago
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1.1 Elastic scattering and inelastic scattering Elastic scattering (Rayleigh scattering) : no change in energy of light EMR induces oscillating electric field in electron cloud around the molecule- which is then re-emitted as a photon j
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If there is a vibration which results in a change in the net polarizability of the electron cloud. (polarizability: a term describes a molecule properties having to do with the deformability of a bond) Inelastic scattering: Scattered photon will be at an energy either greater than or lower than the original energy by an amount equal to the energy of the vibrationa. (only about 1 molecule in 10 8 -10 9 will inelastically scatter photons)
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Stokes Lines: longer wavelength (more intense) Anti-stokes Lines: shorter wavelength = Raman Rayleigh line
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1.2 Wave model Rayleigh scattering Stokes line Anti-Stokes line
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Selection rule 1. There is a change in polarizability during the vibration 2. = 1 For comparison, IR 1. There is a change in dipole moment 2. = 1
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Distortion of bonds becomes easier as they lengthen and more difficult as they shorten. - >change in polarization Distortion of one bond becomes easier as it lengthen and another more difficult as they shorten. - >change in polarization cancel off
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1.3 Intensity of Raman Bands concentration -proportional to concentration Source intensity -directly to source intensity Source wavelength -1/ 4
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2. Instrumentation 2.1 Block diagram
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2.2 Sample handling (pp488-490), simpler than for IR spectroscopy glass can be used for windows, and can use aqueous solution. Fig. 18-8, P489
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2.3 Raman properties Get vibrational spectrum -Complementary with IR -Aqueous solution are accessible to study Problem: -Low efficiency of effect = poor sensitivity -Competition from fluorescence for high fluorescence species Solving problems: -Resonance Raman (selectivity and detectability) -Surface-enhanced Raman (sensitivity and detectability) -Multi-channel detection (detectability) -Near-IR excitation (fluorescence rejection)
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Resonance Raman *
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Near-IR Excitation
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3.1 Vibrational spectral analysis - complementary with IR - molecular structure info - easy and fast 3.2 Quantitative Analysis can be sensitive as fluorescence more selective than fluorescence
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